EP3665168A1

EP3665168A1 - Process to prepare propylene amines and propylene amine derivatives

Info

Publication number: EP3665168A1
Application number: EP18749802.7A
Authority: EP
Inventors: Ina EHLERS; Eike Nicolas Kantzer; Rolf Krister EDVINSSON; Hendrik VAN DAM; Karl Fredrik LAKE; Antoon Jacob Berend Ten Kate; Michiel Jozef Thomas RAAIJMAKERS; Rens VENEMAN; Slavisa JOVIC
Original assignee: Nouryon Chemicals International BV
Current assignee: Nouryon Chemicals International BV
Priority date: 2017-08-11
Filing date: 2018-08-07
Publication date: 2020-06-17
Also published as: WO2019030197A1; KR20200040261A; US11390607B2; CN110997659A; CN110997659B; KR102564338B1; US20200361910A1

Abstract

La présente invention concerne un procédé de préparation de propylène amines de formule NH2-(A-NH-)pR, dans laquelle R est un atome d'hydrogène ou un groupe alkyle, p vaut au moins 1 lorsque R est un groupe alkyle, et au moins 2 lorsque R est un atome d'hydrogène, ou des dérivés ou des précurseurs de ceux-ci, une ou plusieurs unités -NH-A-NH- pouvant être présentes en tant qu'unité d'urée cyclique (I) ou une unité cyclique (II) ou entre deux unités –NH-A-NH- une liaison carbonyle est présente, chaque unité –A- peut être indépendamment une unité alkylène et au moins une unité –A- est une unité -C3H6-, chaque unité -C3H6- pouvant être linéaire ou ramifiée, par réaction (i) d'au moins un composé à fonction hydroxy choisi parmi les composés à fonction alcanolamine, et les composés dihydroxyalkylène, avec (ii) un composé à fonction amine, en présence (iii) d'un agent de distribution d'oxyde de carbone, au moins l'un du composé à fonction alcanolamine, du composé à fonction amine et/ou de l'agent de distribution d'oxyde de carbone contenant au moins une unité alkylène (A) qui est une unité de propylène.The present invention relates to a process for the preparation of propylene amines of formula NH 2 - (A-NH-) p R, in which R is a hydrogen atom or an alkyl group, p is at least 1 when R is an alkyl group, and at least 2 when R is a hydrogen atom, or derivatives or precursors thereof, one or more -NH-A-NH- units that may be present as a cyclic urea unit (I) or a cyclic unit (II) or between two units -NH-A-NH- a carbonyl bond is present, each -A- unit may be independently an alkylene unit and at least one -A- unit is a -C3H6- unit, each -C3H6- unit may be linear or branched, by reaction (i) at least one hydroxy-functional compound selected from alkanolamine compounds, and dihydroxyalkylene compounds, with (ii) an amine-functional compound, in the presence ( iii) a carbon monoxide delivery agent, at least one of the alkano-functional compound laminate, amine-containing compound and / or carbon monoxide delivery agent containing at least one alkylene unit (A) which is a propylene unit.

Description

Process to prepare propylene amines and propylene amine derivatives

The present invention relates to a process for making higher propylene amines (PA), i.e. propylene amines and derivatives (or precursors, which is included by the term derivatives) thereof, like urea derivatives, that contain at least 2 alkylene units of which at least one is a propylene unit, by reacting an hydroxy functional compound with an amine functional compound in the presence of a carbon oxide delivering agent.

Propylene amines consist of two or more nitrogen atoms linked by linear or branched propylene units ( propylene refers to either -CH₂CH₂CH₂- (P) or - CH(CH₃)-CH₂- (iP or isopropylene). Propylene amines can be present in the form of linear chains H₂N(-C3H₆NH)_P-H. For p= 1 ,2,3,4,... these are denoted PDA, DPTA, L-TPTA, L-TPPA, ...

For the branched, the isopropylene, these become iPDA,DiPTA, L-TiPTA, L- TiPPA. Compounds with mixed linear and branched C3 units are also possible.

Propylene amines for the sake of this document include alkylene amines in which at least part of the alkylene units are propylene units. Propyleneamines hence also cover amines wherein other alkylene units can be present, like ethylene units. It should also be noted that a propylene unit can be either linear or branched, wherein the branched propylene can also be denoted as methylethylene or isopropylene.

With three or more alkylene units it is possible to create branched propylene amines such as N(C3H₆)3, TAPA. Two ad acent nitrogen atoms linked by two

ethylene units are called a piperazine , which can also be formed for an isopropylene based amine for example Piperazine rings can be present in longer chains to produce the corresponding cyclic propylene amines. When having linear propylene units, also cyclic structures can be formed like diazocane groups.

Two adjacent nitrogen atoms linked by one propylene unit and one carbonyl

moiety form a cyclic urea (U) . A propylene amine (PA) in which two nitrogen atoms are linked intramolecular by a carbonyl moiety is here referred to as an UPA (urea propylene amine or propylene urea). Replacing the carbonyl moiety with two hydrogen atoms yields the corresponding propylene amine. For example: PU<→PDA, UDPTA<→DPTA, UAPPA<→APPA, UTPTA<→L- TPTA, UTPPA^L-TPPA. Some higher amines host more than one carbonyl moiety, e.g. DU-TPTA the cyclic diurea of tripropylenetetramine. The carbonyl moiety may link nitrogen atoms on two separate molecules. For example H2NC3H6NH-CO-NHC3H6NH2 and replacing the carbonyl moiety with two hydrogen atoms here yields two PDA.

Each amine function in propylene amines and propylene ureas can be primary, secondary or tertiary. Furthermore, a secondary amine can be linear (linear secondary amines, LSA) or cyclic (cyclic secondary amine, CSA).

In the presence of any Br0nsted acid (such as water) propylene amines (PA) can be protonated (PAH⁺). If not otherwise stated the term amine in this document will include both the protonated and unprotonated form. Some propylene amines and urea derivatives thereof are shown below as an illustration. This can naturally be extended to include pentamines, hexamines and so on.

H,N NH,

^¾ H₂ u N H,N N NH,

H

PDA iPDA DPTA

dipropylenetriamine

H,N

Η,Ν^' ~Ν^{' v ^}N^' ~NH, NH,

H H

L-TPTA

DAiP-EDA

diaminoisopropyl EDA

e

tris-aminopropylamine

NH,

-NH,

.NH,

Η,Ν^' HN N- HN N-

H

APP

Aminopropylpiperazine Aminoethyl-1 ,5-diazocane

O O

X X O O

X X

HN N^' ^¾N NH HN N^' ^¾N NH

DUTPTA DU (AE-DPTA)

diurea of tripropylenetetramine diurea of aminoethyldipropyltriamine As to naming of the molecules, PDA stands for propylenediamine, and iPDA for isopropylenediamine, DPTA for dipropylenetriamine, L-TPTA for linear tripropylenetetraamine, DAiP-EDA for diamineisopropyl ethylenediamine. TAPA for triaminopropylamine., AP-EDA for aminopropylethylenediamine, APP for aminopropylpiperazine, DAP-EDA for diaminopropylethylenedaimine, PP-PU fpr piperazinopropyl propyleneurea, PU for propyleneurea, AP-PU for aminopropyl-propyleneurea, DUPTA for the diurea of tripropylenetetramine, DU(AE-DTPA) for the diurea of aminoethyldipropyltriamine When there is a single cyclic urea in the molecule this is indicated by adding a U in front of the name, i.e. UTPTA means the cyclic urea of TPTA, while when there are two cyclic ureas in the molecule this is indicated by DU, i.e. DUTPTA means the internal cyclic diurea of TPTA. If there is a number indicated for the U this refers to the amino group where the U group is located. There is one exception to this naming and that is that instead of UPDA the abbreviation PU is used, which stand for propyleneurea.

The manufacturing of propylene amines is presently disclosed to be done by two routes. These are the reaction of dichloropropanes (1 ,2- and 1 ,3- dichloropropane) with NH₃ or the reaction of an alkylene amines with acrylonitrile and subsequent hydrogenation.

There are however many limitations in the above state of the art routes, like chloride based processes have severe limitations if only because CI-C3H6-NH2 self-polymerizes very easily, and chloride based processes lead to salt (waste) formation.

The application of acrylonitrile involves a tricky hydrogenation reaction and side product formation from addition reactions with amines (also the intermediate C=N is amine reactive). Again this process suffers from poor control and selectivity.

Furthermore, handling of hazardous acrylonitrile is a risk, because acrylonitrile is a.o. highly flammable and toxic at low doses, can undergo explosive polymerization, is a suspected carcinogenic compound, evaporates quickly at room temperature (20 °C) to easily reach dangerous concentrations.

AlChEAnnual Meeting Conference 2012 'In Situ synthesis of useful amines for CO2 capture from piperazine' discloses the oxazolidinone formation for an ethanolamine and a propanolamine and next shows how an oxazolidinone can react with an amine

US 4,503,250 discloses the formation of linear polyalkylene amines in good yield by reaction of an alkyleneamine or ammonia with an alcohol or alkanolamine in the presence of derivative of carbonic acid. The alkanolamine covers propanolamines but only ethylene-based explicit examples are mentioned. The alkyleneamine also covers propylene amines, but again only ethylene-based explicit examples are given. None of the Examples mentions the reaction of propylene-based amines or alcohols either.

US 5,491 ,263 discloses the formation of substituted ethylenediamines such as substituted EDA, DETA, TETA, TEPA, PEHA, E-100 and piperazine by reacting oxazolidinones with alkanolamines or secondary amines. The document also suggests isopropylene amine preparations, but such reactions are not explicitly disclosed and hence not enabled, the document seems to more focus on reacting oxazolidinones having a substituent on the nitrogen atom to create branched amines (called dimers and trimers). Though all the above documents make a suggestion that the reactions disclosed in them could be performed to prepare propyleneamines, none of them actually demonstrates such reactions or gives the conditions needed for them to be carried out

It should be noted that WO2013/1 10092 discloses in Example 7 the oxazolidinone structures of monoisopropanol amine or monopropanol amine and their reaction product with piperazine, i.e. an amine-functional compound with a terminal cyclic urea unit, under non-aqueous conditions.

There is a demand for propylene amines and hence there is a need for a process for selectively making such propylene amines with an improved yield. Especially there is a need for a process to prepare specific higher linear propylene amines with good yield and selectivity. Furthermore there is a need for such a process for making higher propylene amines that does not co- generate large amounts of waste salt.

The present invention now provides a process to prepare propylene amines of the formula NH₂-(A-NH-)_PR , wherein R is a hydrogen atom or an alkyl group, p is at least 1 when R is an alkyl group, and at least 2 when R is a hydrogen atom, or derivatives or precursors thereof wherein one or more units -NH-A-NH- may be present as a cyclic urea unit

or a cyclic unit

or between two units -NH-A-NH- a carbonyl bond is present each unit -A- can be independently an alkylene unit and at least one unit -A- is a -C3H_6- unit, wherein each -C3H6- unit can be linear or branched, by reacting (i) at least one of a hydroxy-functional compound chosen from the alkanolamine- functional compounds, and dihydroxyalkylene compounds, with (ii) an amine- functional compound in the presence of (iii) a carbon oxide delivering agent, wherein at least one of the alkanolamine-functional compound, the amine compound and/or the carbon oxide delivering agent contains at least one alkylene unit (A) that is a propylene unit.

The process of the invention solves all the above indicated problems and leads to the production of propylene amines in good yield and selectivity. The process is moreover based on chemical compounds that have a better HSE (health safety and environment) profile (ethanol- and propanolamines e.g. have a very low mutagenic potential) than the mentioned state of the art processes. Besides, the present process provides for increased flexibility in producing different types of higher amines, like, combining different alkylene units, like ethylene and propylene and cyclic units in a very controlled manner under relatively mild reaction conditions.

The product of the process of the invention is in this document sometimes referred to as polypropylene amine as well as as propylene amine. Still these terms refer to the same group of compounds. Furthermore as should also be clear from the embodiments, a product propyleneamine or polypropylene amine may contain hydroxyl groups, and may contain a terminal alkyl group. Selecting the right molar ratios between the carbon oxide delivering agent, amine-functional compound and hydroxy-functional compound, was found to have an effect on conversion, selectivity and yield in the process of the invention.

The molar amount of either one of these carbon oxide delivering agent, amine- functional compound and hydroxy-functional compound is determined by the reactants in the process, independent of the dosing regime used for the reactants.

In a preferred embodiment the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 0.6 to 1 .

It was found that when adding at least 0.6 molar equivalents of carbon oxide delivering agent on amine-functional compound, the yield of propylene amines increases considerably and also the amount of side products decreases, i.e. the selectivity of the reaction towards specific propylene amines increases.

In this embodiment it is more preferred that the molar amount of carbon oxide delivering agents on amine-functional compounds is between 0.7 and 20 molar equivalents of carbon oxide delivering agent on moles of amine functional compound, and yet more preferably it is between 0.7 and 6:1 , most preferably between 0.8:1 and 3:1 . In another preferred embodiment the molar ratio of hydroxy-functional compound to amine-functional compound is at least 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 0.05:1 . In such embodiments the yield of propylene amines is also high. In this embodiment, more preferably the molar ratio of hydroxy-functional compound to amine-functional compound is between 0.8 and 5:1 and the molar ratio of carbon oxide delivering agent to amine functional compound is between 0.2:1 and 20:1 .

Yet even more preferably the molar ratio of hydroxy-functional compound to amine-functional compound is between 1 :1 and 2:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is between 0.7:1 and 3:1

To achieve a high selectivity of propylene amine product on starting materials, especially on hydroxy-functional compound, in another preferred embodiment the molar ratio of hydroxy-functional compound to amine-functional compound is between 0.05:1 and 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is higher than the molar ratio of hydroxy- functional compound to amine-functional compound.

In this embodiment, more preferably the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 10% higher, even more preferably at least 50%, than the molar ratio of hydroxy-functional compound to amine-functional compound. In yet another more preferred embodiment the molar ratio of hydroxy-functional compound to amine-functional compound is between 0.1 and 0.5. It should be noted that compounds exist that contain more than one carbonyl group that can be released from the molecule for transfer to the hydroxy- functional compound, such as for example DU-TPTA. When determining the molar ratio for such compounds there should be an adjustment for the molar amount of carbon oxide they can release for transfer to the hydroxy-functional compound. Accordingly, 1 mole of DU-TPTA should be considered 2 moles of carbon oxide delivering agent.

The reaction mixture characterized by containing as reactants hydroxy- functional compound, amine-functional compound and carbon oxide delivering agent can be roughly represented by below (non-limiting) schemes.

Schemes IA and 1 B: Amine functional compound is a primary ethyleneamine, respectively propyleneamine

H₂N R₂ F

I Addition of CO to the ethanolamine to form the 2-oxazolidinone ring

II Chain extension by ring opening by primary amine

III Removal of carbonyl group to form the ethylene amine

IV Intramolecular rearrangement of carbonyl group

V Hypothetical direct uncatalyzed amination

H,N-R,

NH OH NH HN

A VJ VJ

I Addition of CO to the propanolamine to form the cyclic carbamate

II Chain extension by ring opening by primary amine

III Removal of carbonyl group to form the propylene amine

IV Intramolecular rearrangement of carbonyl group

V Hypothetical direct uncatalyzed amination chemes 2A and 2B: Amine functional compound is a Cyclic Secondary Amine

HN N— R₂

I Addition of CO to the ethanolamine to form the 2-oxazolidinone ring

II Chain extension by ring opening by cyclic secondary amine

III Removal of carbonyl group to form the ethylene amine

V Hypothetical direct uncatalyzed amination

I Addition of CO to the propanolamine to form the cyclic carbamate

II Chain extension by ring opening by cyclic secondary amine

III Removal of carbonyl group to form the propylene amine

V Hypothetical direct uncatalyzed amination A number of reactions take place in parallel when heating a mixture of a carbonyl source, a hydroxy-functional compound and an amine-functional compound. Without being bound to theory this can be summarized in two main reaction steps each composed of multiple sub steps: 1 ) the activation of the alcohol function (A) by the carbonyl group, the carbamate compound (B) is assumed to be an intermediate, 2) the activated alcohol function is replaced by an amine (C) to give a chain extended primary addition product (D). In the presence of ammonia a conversion of the alcohol function to an amine function without giving a chain extension can take place as well. The product (D) may undergo further reaction leading to secondary CO containing products as illustrated by reaction IV and product (F). Such products include but are not limited to cyclic propylene urea derivatives but include all kinds of CO containing amines as for example illustrated in below examples of CO delivering agents. Optionally the CO groups can be removed leading to the formation of a propylene amine (E).

The dihydroxyalkylene compound in preferred embodiments is selected from the group of dihydroxyethane, 1 ,2-dihydroxypropane and 1 ,3-dihydroxypropane.

The alkanolamine-functional compound is a compound containing a hydroxyl group linked via an alkylene to an amine group that optionally may be present as its carbamate equivalent. Generally the alkanolamine-functional compound is of the following formula

OH-(A-NH-)_qR

Where R in embodiments is a substituted or unsubstituted alkyl group which also can contain unsaturated moieties and heteroatoms such as oxygen and nitrogen or a hydrogen atom, q is at least 1 , and A is an alkylene unit, and at least one A is propylene. In one embodiment R is a proton or hydroxyalkyl group. Examples of alkanolamine functional compounds include

PPA

Hydroxy isopropyl Hydroxypropyl ethylene urea HE-PU aminoethyl piperazine Hydroxyethyl propyleneurea

As to naming convention, MPA stands for monopropanolamine, 1 -MiPA stands for 1 -aminopropan-2-ol, 2-MiPA stands for 2-aminopropan-1 -ol, CMPA stands for 1 ,3-oxazinan-2-one, 5-Me— CMEA stands for 5-methyloxazolidin-2-one, HEiP-iPU stands for hydroxyisopropylisopropyleneurea, APPA stands for aminopropylpropanolamine (also referred to as hydroxypropylpropyleneamine), HiP-AEP stands for hydroxyl isopropyl aminoethylpiperazine, HP-EA stands for hydroxypropyl ethyleneurea and HE-PU stands for hydroxyethyl propyleneurea.. By using the letter C it is indicated that a cyclic carbamate ring is present in the molecule. By using the letter U it is indicated that a cyclic urea ring is present in the molecule.

The carbon oxide delivering agent is a compound containing a carbonyl moiety that can be transferred to an alkanolamine functional compound leading to the formation of a cyclic carbamate, such as CMPA or that can be transferred to an amine leading to the formation of the corresponding cyclic urea. Next to cyclic compounds linear carbamates and ureas may form as well. Carbon oxide delivering agents within the scope of the present invention include organic compounds in which a carbonyl moiety is available for being transferred as described above. Organic compounds in which a carbonyl moiety is available for being transferred include carbon dioxide, and urea and derivatives thereof; linear and cyclic alkylene ureas, especially cyclic urea, mono or di-substituted alkylene ureas, alkyl and dialkyl ureas, linear and cyclic carbamates, organic carbonates and derivatives or precursors thereof. Such derivatives or precursors may for example include ionic compounds such as carbonate or bicarbonate salts, carbamic acids and associated salts, that can be converted, in some embodiments in situ in the process of the invention, into their non-ionic counterparts, for example into linear and cyclic carbamate or urea compounds. When such ionic compounds are used in the present invention, they are organic hydrocarbon-based carbonate, bicarbonate or carbamate salts. Preferably the CO delivering agent is CO2, a cyclic alkylene urea or cylic alkylene carbamate, optionally wherein part of the alkylene is propylene, or urea or propylene carbonate, more preferably the carbon oxide delivering agent is at least partly added as carbon dioxide or urea. The carbon oxide delivering agent can be present in the process in the same molecule as the amine functional or the alkanolamine functional compound by using the aforementioned urea or carbamate compounds. Examples of carbon oxide delivering agents include

iPDA carbamate PDA carbamate Zwitterion PDA carbamate PDA dicarbamate Zwitterion

PDA bicarbonate PDA carbonate

CMPA diaminopropyl AP AP carbamate carbonate DAiPC

5-Me-CMEA AiP AiP carbamate

PU DAPU

CAPPA UAPPA

DUTPTA

of U1TPTA

ydroxypropyl DPTA

In the above drawing PDA stands for propylenediamine (1 ,3-diamino propane), iPDA stands for isopropylenediamine (1 ,2-diamino propane), CMPA stands for the carbamate of monopropanolamine, DAPC for diaminopropyl carbonate, DAiPC for diaminoisopropyl carbonate, AP AP carbamate and AIP AIP carbamate for the carbamate of two aminopropanols or aminoisopropanols, 5- Me-CMEA for the carbamate of isopropanolamine, PU for propyleneurea, DAPU stands for diaminopropyl urea, CAPPA stands for the carbamate of aminopropylpropanolamine and UAPPA stands for the urea of aminopropylpropanolamine, AiP-iPU stands for aminoisopropyl isopropyleneurea, UDPTA for the urea of dipropylene triamine, U1 TPTA stands for the terminal urea of tripropylene tetramine, and DUTPTA stands for the 1 ,3- diurea of tripropylene tetramine.

The carbon oxide delivering agent is most preferably added to the reaction in the form of carbon dioxide, urea, the carbamate derivative of the alkanolamine- functional compound or the urea derivative of the amine-functional compound, or a combination of these.

Heating a suitable mixture of an alkanolamine-functional compound, an amine that is not tertiary and a carbon oxide delivering agent to a relatively high temperature provides a way to produce a higher amine and CO containing derivative thereof that can serve as a carbon oxide delivering agent.

The amine-functional compound is a compound containing one or more amine groups, preferably at least two amine groups, and no alcohol groups.

In many embodiments the amine-functional compound is a compound of the formula

RRN-(A-NR-)_rR wherein r is at least 1 , each R is independently as defined above for the alkanolamine compound provided that it does not contain any hydroxyl groups, i.e. R in embodiments is a substituted or unsubstituted alkyl group which also can contain unsaturated moieties and heteroatoms such as oxygen and nitrogen or a hydrogen atom, and preferably all R groups are hydrogen or one terminal R is an alkyl group while the other R groups are a hydrogen atom, and A is as defined above for the alkanolamine compound. Many compounds illustrated above as propylene amine compounds are amine- functional compounds as well.

In a preferred embodiment the amine-functional compound is a compound containing at least two amine groups. Even more preferred the amine-functional compound contains at least two amine groups that are independently a primary amine group or cyclic secondary amine group, and optionally more amine groups that may be primary, secondary and/or tertiary amines wherein the amine groups within the compound are linked to one another via alkylene groups, and optionally some by a carbonyl moiety, and/or an additional alkylene group (to give a methylsubstituted or unsubstituted piperazine unit, a diazocane unit, or urea unit in the amine functional compound).

In another preferred embodiment the amine-functional compound is a compound of the formula R-NH₂, wherein R is a substituted or unsubstituted, linear or branched alkyl group which also can contain unsaturated moieties and heteroatoms such as oxygen and nitrogen but does not contain a hydroxyl group. Yet even more preferred R is an alkyl group, that may be branched or linear, and that in embodiments contains 6 to 22 carbon atoms.

In a further preferred embodiment in the process the alkanolamine-functional compound is of the formula OH-(A-NH-)_qH wherein q is at least 1 and the amine-functional compound is of the formula NH₂-(A-NH-)_rH wherein r is at least 1 , wherein the sum of q+r is at least 2, more preferably q+r is at least 3, each A unit is independently a -C2H - unit or -C3H6- unit and at least one A unit is a -C3H6- unit, and each C3H6 unit can be linear or branched, and wherein optionally one or more q or r units may be present as a cyclic propylene urea, cyclic propylene carbamate, methylsubsituted piperazine unit, diazocane unit, or unsubsituted piperazine unit. In another preferred embodiment the alkanolamine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using a carbamate adduct and/or the amine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using an urea adduct.

In embodiments wherein the amine-functional compound is a compound

containing a terminal cyclic unit , i.e. a compound containing the above cyclic unit wherein at least one nitrogen is bound to a hydrogen atom, the process of the present invention is preferably performed in a liquid that contains water, even more preferably at least 75 wt% of water on total liquid weight. In yet another preferred embodiment wherein the amine-functional

— N N- compound is a compound containing a terminal cyclic unit , the molar ratio of water to the amine-functional compound containing the terminal cyclic unit is greater than 0.2:1 , preferably greater than 0.5:1 and most preferably greater than 1 :1 .

In embodiments wherein in the reactants (and consequently products) of the process of the invention one or more units -NH-C2H4-NH- are present as a

cyclic unit , such as in embodiments a unsubstituted or methylsubstituted piperazine unit the reaction is preferably performed in a liquid that comprises water. Examples of embodiments wherein one or more of the units -NH-A-NH- are present as a piperazine unit is when the amine-functional compound is piperazine (PIP), aminoethylpiperazine (AEP), or diaminoethylpiperazine (DAEP), piperazinoethyl ethylenediamine (PEEDA), or a linear urea derivative thereof or 2-methylpiperazine, 2,5-dimethylpiperazine, 2-(3-methylpiperazin-1 - yl)ethan-1 -amine, 2-(2,5-dimethylpiperazin-1 -yl)ethan-1 -amine, 2,2'-(2- methylpiperazine-1 ,4-diyl)bis(ethan-1 -amine), 2,2'-(2,5-dimethylpiperazine-1 ,4- diyl)bis(ethan-1 -amine), N1 -(2-(3-methylpiperazin-1 -yl)ethyl)ethane-1 ,2-diamine, N1 -(2-(2,5-dimethylpiperazin-1 -yl)ethyl)ethane-1 ,2-diamine or a linear urea derivative thereof or when the alkanolamine-functional compound is an isopropanolamine, 2-amino-1 -propanol or 1 -amino-2-propanol or diisopropanolamine . Even more preferably when cyclic/piperazine units are present in the reactants or products of the process of the invention the liquid comprises at least 75 wt-% of water on total liquid weight. In yet another even more preferred embodiment the molar ratio of water to the amine-functional compound is greater than 0.2:1 , preferably greater than 0.5:1 and most preferably greater than 1 :1 .

When preparing propyleneamines that do not contain piperazine units and/or

other cyclic units , i.e when using reactants that are free from cyclic and/or piperazine units, the process in other preferred embodiments is carried out in water, with a molar ratio of water: carbon oxide delivering agent of from 0.01 :1 to 2:1 , more preferably a molar ratio of water : carbon oxide delivering agent is between 0.05:1 and 1 :1 . It is yet even more preferred that water is added or removed during the process intermittently, semi-continuously or continuously to maintain the amount of water such that the molar ratio of water : carbon oxide delivering agent remains in the desired range such as for non-cyclic propylene amines preparations of from 0.01 :1 to 2:1 .

When preparing propylene amine compounds having at least 3 alkylene units and using carbon dioxide as the carbon oxide delivering agent, it is a beneficial embodiment of the process to during the reaction wherein the amine-functional compound reacts with CO2 add an auxiliary compound selected from ethylenediamine (EDA), propylenediamine (PDA), monoethanolamine (MEA), monopropanolamine (MPA) and mixtures thereof, the molar ratio of auxiliary compound to amine-functional compound being at least 0.02:1 . In this embodiment, more preferably the molar ratio of auxiliary compound to amine-functional compound is at least 0.05:1 , in particular at least 0.1 :1 , and/or at most 10:1 . Yet even more preferred the molar ratio between CO2 and -NH-A- NH- moieties in the amine-functional compound is at least 0.5:1 and/or at most 500:1 .

More specifically the above relates to a process to prepare propylene amines or cyclic urea adducts thereof, which process comprises the steps of

a) manufacturing a cyclic urea adduct of an alkylene amine compound and/or alkanolamine compound comprising at least one -NH-A-NH- moiety and at least two A moieties wherein at least one alkylene (A) unit in the product is a propylene unit, wherein the alkylene amine compound is reacted with CO2 in the presence of an auxiliary compound selected from ethylene diamine (EDA), propylenediamine (PDA or iPDA) monoethanolamine (MEA), monopropanolamine (MPA or MiPA) and mixtures thereof, the molar ratio of auxiliary compound to amine-functional compound being at least 0.02:1 , and b1 ) where the cyclic urea adduct of an alkylene amine compound is a cyclic urea adduct of alkylene amine, reacting the cyclic urea adduct of alkylene amine with an alkanolamine-functional compound, or a urea- or carbamate additive thereof, or

b2) where the cyclic urea adduct of an alkylene amine compound is a cyclic urea adduct of an alkanolamine, reacting the cyclic urea adduct of an alkanolamine with a alkylene amine compound, or a urea- or carbamate additive thereof. Using the process of the invention it is well possible to prepare tailored mixtures of straight chain and non-straight chain propylene amines wherein the non- straight chain propylene amines can be branched or cyclic propylene amines by a smart selection of the starting material amine-functional compound, alkanolamine-functional compound and carbon oxide delivering agent. This because substantially any branched and cyclic raw materials find their way into the product without losing their branching or cyclic structure and also no substantial new levels of branching and cyclization occur during the process of the invention Accordingly, the present invention also provides a process of preparing a mixture of straight-chain propyleneamines and non-straight-chain propyleneamines selected from branched propyleneamines and cyclic propyleneamines, or the urea derivatives thereof, comprising the step of reacting amine-functional compound with alkanolamine-functional compound in the presence of a carbon oxide delivering agent, wherein

a) amine-functional compound comprising a combination of straight-chain amine-functional compound and non-straight-chain amine-functional compound is reacted with straight-chain alkanolamine-functional compound, or

b) straight-chain amine-functional compound is reacted with alkanolamine- functional compound comprising a combination of straight-chain alkanolamine- functional compound and non-straight-chain alkanolamine-functional compound, or

c) amine-functional compound comprising a combination of straight-chain amine-functional compound and non-straight-chain amine-functional compound is reacted with alkanolamine-functional compound comprising a combination of straight-chain alkanolamine-functional compound and non-straight-chain alkanolamine-functional compound

In a more preferred embodiment for making tailored mixtures, the amine- functional starting material comprises non-straight-chain amine-functional compound comprising a cyclic amine-functional compound selected from the group of piperazine or methyl substituted piperazine or an alkyleneamine derivative of either of those such as aminoethylpiperazine, diaminoethylpiperazine, piperazinoethylpiperazine, piperazino- ethylethylenediamine, and mixtures thereof, in particular piperazine aminopropylpiperazine and/or aminoethylpiperazine.

The amine-functional starting material comprises non-straight-chain amine- functional compound comprising a branched amino-functional compound compri tiary nitrogen atom, e.g., a compound of the formula

wherein each n independently is 0 or an integer, in particular 1 , 2, 3, or 4.

The straight-chain amine-functional compound may comprises one or more compounds of the formula HN-(A-NH)_rH, wherein r is at least 1 , in particular in the range of 1 to 10, more in particular 1 to 5

The non-straight-chain ethanolamine-functional compound may comprise a cyclic alkanolamine-functional compound, e.g., a compound selected from the group of hydroxyalkyl derivatives of aminoethylpiperazine (AEP), e.g., piperazinoethylmonoethanolamine (PE-MEA).

The non-straight-chain alkanolamine-functional compound may furthermore comprise a branched alkanolamine-functional compound comprising at least one tertiary nitrogen atom, for example a compound of the formula

N[(A-(NH-A)_n-OH)]_m[(A-(NH-A)p-NH₂)]3-m,

wherein m is 1 , or 2, or 3, each n independently is an integer, in particular 1 , 2, 3, or 4, and each r independently is 0 or an integer, in particular 1 , 2, 3, or 4, in particular a compound m is 1 , n is 1 , and p is 0.

The straight-chain ethanolamine-functional compound may comprises compounds of the formula HO-(A-NH)_q-H wherein q is at least 1 , in particular in the range of 1 to 10, more in particular 1 to 5.

In a preferred embodiment for making tailored mixtures the ratio of the total amount of piperazine moieties and methylated piperazine moieties in the starting materials to the total amount of such moieties in the product from the reaction is in the range of 0.7:1 to 1 .3:1 , in particular in the range of 0.8:1 to 1 .2:1 , more in particular in the range of 0.9:1 to 1 .1 :1 .

In another preferred embodiment for making tailored mixtures the ratio of the total amount of tertiary amine moieties of the formula N(A-)₃ in the starting material to the total amount of tertiary amine moieties of the formula N(A-)₃ in the product from the reaction generally is in the range of 0.7:1 to 1 .3:1 , in particular in the range of 0.8:1 to 1 .2:1 , more in particular in the range of 0.9:1 to 1 .1 :1 .

In the process of the invention a step may be present in which a cyclic urea adduct of an alkyleneamine compound is first made, the alkyleneamine compound having at least one linear -NH-A-NH- group, and at least one alkylene unit (A) is a propylene unit, and the process comprises the steps of

- in an absorption step contacting a liquid medium comprising an alkyleneamine compound having a linear -NH-A-NH- group with a CO₂-containing gas stream at a pressure of 1 -20 bar, resulting in the formation of a liquid medium into which CO₂ has been absorbed,

- bringing the liquid medium to cyclic urea formation conditions, and in an urea formation step forming cyclic urea adduct of the alkyleneamine compound, urea formation conditions including a temperature of at least 120°C, wherein the total pressure at the end of the urea formation step is at most 20 bar, wherein the temperature in the absorption step is lower than the temperature in the urea formation step.

Contrary to what was expected it was found very well possible to get a good cyclic urea formation under the above mild conditions and under these conditions a suitable cabon oxide delivering agent can be made for use in the further process of the present invention.

Preferably the CO2-containing gas stream comprises at least 95 vol.% of CO₂.

The step of contacting the liquid medium with the CO₂-containing gas steam in the absorption step is carried out preferably at a temperature between 0°C and 200°C,in particular at a temperature of at most 190°C, more in particular at most 150°C, or at most 130°C, more in particular at most 1 10°C and preferably at a value of at least at least 20°C, in particular at least 40°C.

The maximum total pressure in the absorption step is preferably between 1 and 15 bara, more in particular between 1 and 10 bara, even more in particular between 1 and 3 bara. The temperature in the urea formation step is suitably at least 140°C, in particular at least 150°C, more in particular at least 170°C and preferably at most 400°C, in particular at most 300°C, more in particular at most 250°C, or even at most 220°C and the urea formation step is preferably carried out in a closed vessel or a vessel wherein the volume of the liquid medium in the vessel makes up at least 50% of the total volume of the vessel (including head space), in particular at least 70%, more in particular at least 85%.

Preferably the pressure at the end of the cyclic urea formation step is below 15 bar, in particular below 10 bar, in some embodiments below 5 bar, or even below 3 bar.

In another preferred embodiment urea is used as the carbon oxide delivering agent. The urea is dissolved or dispersed as solid in a vessel together with the liquid comprising alkanol and/or alkylene amine. The temperature in the urea formation step is suitably at least 140°C, in particular at least 150°C, more in particular at least 170°C and preferably at most 400°C, in particular at most 300°C, more in particular at most 250°C, or even at most 220°C. The maximum total pressure in the urea reaction step is preferably between 1 and 100 bara, more in particular between 1 and 50 bara, even more in particular between 1 and 10 bara.

The reaction time is preferably between 1 minute and 10 hours, more preferably between 30 minutes and 5 hours.

The cyclic urea or cyclic carbamate formation can be carried out in a closed vessel in which the released ammonia causes a pressure to build up. At the end of the reaction ammonia has to be released and the resulting gas stream is suitably treated to remove or recover the ammonia for further use. More preferably it is carried out in a vessel in equipped in which ammonia is continuously, semi-continuously or on one or several occasions removed from the system and suitably treated or recovered. The process of the present invention in embodiments may in embodiments be performed as an integrated process for manufacturing polypropylene amine compounds selected from the group of propyleneamines and hydroxyl- functional propyleneamines comprising the steps of

- an adduction step providing a CO2 adduct of a starting compound comprising a -NH-A-NH- moiety or a -NH-A-OH moiety, or HO-A-OH,

- in a reaction step reacting a hydroxy-functional compound selected from the group of alkanolamines, dihydroxyethane, 1 ,2-dihydroxypropane and 1 ,3- dihydroxypropane with an amine-functional compound, wherein at least part of the total of hydroxy-functional compounds and amine-functional compounds is provided in the form of a CO2 adduct, to form CO2 adduct of a polypropylene amine compound,

- in an elimination step converting CO2 adduct of polypropylene amine compound to the corresponding polypropylene amine compound,

wherein a fraction comprising a recycle compound comprising a -NH-A-NH- moiety or a -NH-A-OH moiety, or HO-A-OH, or CO₂ adducts thereof, is provided from the end of the reaction step or the elimination step to the adduction step or to the reaction step,

the recycle compound having per molecule on average fewer of the total of - NH-A-NH- moieties and -NH-A-OH moieties than the polypropylene amine compound.

In the above integrated process, the adduction step may comprise an absorption step wherein gaseous CO2 is reacted with a starting compound comprising a -NH-A-NH- moiety or a -NH-A-OH moiety, or HO-A-OH, to form a CO₂ adduct thereof. In the above integrated process, the adduction step may comprise the step of reacting starting compound comprising -NH-A-NH- moiety or a -NH-A-OH moiety, or HO-A-OH with a carbon oxide delivering agent which can transfer a carbonyl group to the starting compounds, resulting in the formation of CO2 adducts thereof.

The elimination step in the integrated process may comprise a desorption step in which the CO2 adduct of polypropylene amine compound is reacted with water to form CO2 and the corresponding propylene amine compound.

In another embodiment the elimination step may comprise a caustic treatment step in which CO2 adduct of polypropylene amine compound is reacted with an inorganic base, resulting in the formation of a polypropylene amine compound and a carbonate salt.

In yet another embodiment the elimination step may comprise a CO2 transfer step, wherein the carbonyl group from the CO2 adduct of the polypropylene amine compound is transferred to a compound having a -NH-A-NH- moiety or a NH-A-OH moiety, or HO-A -OH.

In the integrated process the adduction step may comprise an absorption step and the elimination step may comprise a desorption step, wherein CO2 formed in the desorption step is provided at least in part to the absorption step.

In another embodiment the adduction step comprises an absorption step and the elimination step comprises a desorption step, and wherein stripping gas withdrawn from the desorption step is subjected to a CO2 removal step and recycled at least in part to the desorption step. Preferably, the stripping gas containing CO2 is removed from the desorption step and provided to absorption step, where CO2 is absorbed from the CO2- containing stripping gas, and stripping gas from which CO2 has been removed is withdrawn from the absorption step and provided to the desorption step.

In an embodiment of the integrated process a separation step is provided after the elimination step, the separation step yielding a fraction comprising a recycle compound comprising a -NH-A-NH- moiety or a -NH-A-OH moiety, or HO-A- OH, or CO2 adducts thereof, which fraction is provided in its entirety or in part to the adduction step or to the reaction step,

the recycle compound having per molecule on average fewer of the total of -NH-A-NH- moieties and -NH-A-OH moieties than the polypropylene amine compound, the recycle compound comprising starting compounds and optionally intermediate compounds, the separation step further yielding a product fraction of polypropylene amine compounds.

Preferably, a separation step is provided after the reaction step and before the elimination step, the separation step yielding a fraction comprising a recycle compound comprising a -NH-A -NH- moiety or a -NH-A-OH moiety, or HO-A- OH, or CO2 adducts thereof, which fraction is provided in its entirety or in part to the adduction step or to the reaction step, the separation step further yielding a fraction comprising CO2 adduct of polypropylene amine compounds, which fraction is provided to the elimination step. In another preferred embodiment of the integrated process the elimination step comprises a first elimination step and one or more further elimination steps, wherein the elimination steps are independently selected from the group of - a desorption step in which the CO2 adduct of polypropylene amine compound is reacted with water to form CO2 and the corresponding ethylene amine compound, - a caustic treatment step in which CO2 adduct of polypropylene amine compound is reacted with an inorganic base, resulting in the formation of a polypropylene amine compound and a carbonate salt, and

- a CO2 transfer step, wherein the carbonyl group from the CO2 adduct of the polypropylene amine compound is transferred to a compound having a -NH-A -

NH- moiety or a NH-A-OH moiety, or HO-A-OH,

wherein the first elimination step converts part of the CO2 adducts of polypropylene amines present in the feed thereto into the polypropylene amine compounds, while part of the CO2 adducts of polypropylene amines present in the feed to the first elimination step is not converted in the first elimination step, and is provided to a further elimination step.

Even more preferred, the first elimination step is a desorption step or a CO2 transfer step and the further elimination step is a desorption step or a caustic treatment step, wherein the steps are not the same.

In a further preferred embodiment the elimination step yields a product comprising polypropylene amine compounds and CO2 adducts of polypropylene amine compounds, and this product is provided to a separation step where a fraction comprising CO2 adducts of polypropylene amine compounds is separated from the polypropylene amine compounds, and processed in one or more of the following manners:

- it is subjected at least in part to purification and further separation steps,

- it is recycled at least in part to the elimination step,

- it is provided at least in part to a further elimination step which is carried out under more stringent conditions than the first elimination step, and comprises, e.g., a treatment with a strong inorganic base,

- it is provided at least in part to the reaction step. In an embodiment the starting materials are provided to the reaction step via one of the following methods:

- the amine-compound is provided in its entirety or in part to the adduction step where it is converted into its CO2 adduct, which is then provided to the reaction step, with the hydroxy-functional compound being provided to the reaction step,

- the hydroxy-functional compound is provided in its entirety or in part to the adduction step where it is converted into its CO2 adduct, which is then provided to the reaction step, with the amine-functional compound being provided to the reaction step,

- the hydroxy-functional compound and the amine-functional compound are both provided to the adduction where they are converted in their entirety or in part to their CO2 adducts, which are provided to the reaction step.

In another embodiment the adduction step comprises an absorption step and the elimination step comprises a desorption step, and wherein a stream comprising CO2 is withdrawn from the desorption step and provided to the absorption step and a stream comprising water is withdrawn from the absorption step and provided to the desorption step. A stream comprising water may be withdrawn from the reaction step and provided to the elimination step in the integrated process.

A separation step may be provided after the reaction step and before the elimination step and independently a further separation step may be provided after the elimination step.

In yet another preferred embodiment of the integrated process, the process comprises the steps of

- providing a starting compound comprising a -NH-A-NH- moiety or a -NH-A- OH moiety, or HO-A-OH to an absorption step where it is combined with CO2 and reacted to form a CO2 adduct, - providing the CO2 adduct to a reaction step where it is reacted with a further reactant, the reactants in the reaction step being a hydroxy-functional compound selected from the group of alkanolamines and dihydroxyalkylenes, and an amine-functional compound, wherein at least part of the total of hydroxy-functional compounds and amine-functional compounds is provided in the form of a CO2 adduct, to form a product comprising a CO2 adduct of a polypropylene amine compound,

- providing the product comprising a CO2 adduct of a polypropylene amine compound to a desorption step, where it is contacted with a stripping gas, and withdrawing a CO2-containing stripping gas from the desorption step and providing it to the absorption step,

- withdrawing a stripping gas from which CO2 has been absorbed from the absorption step and providing it to the desorption step,

- providing the product from the desorption step to a separation step, which yields a starting material fraction which is provided to the absorption step or to the reaction step, the separation step further yielding a product fraction of polypropylene amine compounds which is withdrawn for the separation step, and a fraction comprising CO2 adducts of polypropylene amine compounds, which is provided to the desorption step or to the reaction step.

Alternatively in yet another preferred embodiment the integrated process may comprise the steps of

- providing a starting compound comprising a -NH-A-NH- moiety or a -NH-A- OH moiety, or HO-A-OH to an absorption step where it is combined with CO2 and reacted to form a CO2 adduct,

- providing the CO2 adduct to a reaction step where it is reacted with a further reactant, the reactants in the reaction step being a hydroxy-functional compound selected from the group of alkanolamines and dihydroxyalkylenes, and an amine-functional compound, wherein at least part of the total of hydroxy-functional compounds and amine-functional compounds is provided in the form of a CO2 adduct, to form a product comprising a CO2 adduct of a polypropylene amine compound,

- providing the product comprising a CO2 adduct of a polypropylene amine compound to a separation step, which yields a starting material fraction which is provided to the absorption step or to the reaction step, with the remainder being provided to a desorption step,

- in the desorption step contacting the remainder from the separation step with a stripping gas, and withdrawing a CO2-containing stripping gas from the desorption step and providing it to the absorption step,

- providing the product from the desorption step to a further separation step which yields a product fraction of polypropylene amine compounds which is withdrawn for the separation step, and a fraction comprising CO2 adducts of polypropylene amine compounds, which is provided to the desorption step or to the reaction step.

Inorganic bases are Lewis or Br0nsted bases that do not contain a C-C bond and preferably are stong bases that have a pKb of less than 1 .

The reactor(s) employed in the process of the invention can be any suitable reactor including continuously stirred tank reactor, pipeline reactor, tubular or multi-tubular reactor. The reactor may be adiabatic or equipped with external or internal heating devices. Feed may be single point or split into multiple points. It can consist of multiple stages with inter-stage heat exchange.

The process is preferably performed at a temperature of at least 100°C. The temperature should preferably be lower than 400°C. More preferably the temperature is between 200 and 360 °C. Even more preferably the temperature is between 230 and 340 °C. Most preferably the temperature is between 250 and 310°C. In embodiments where the alkanolamine-functional compound is monoethanolamine or monopropanolamine, 2-amino-1 -propanol and/or 1 - amino-2-propanol and/or 3-amino-1 -propanol the most preferred temperature range is between 230 and 290 °C.

The reaction time during the process is in an embodiment between 5 minutes and 15 hours, preferably between 0.5 and 10 hours, more preferably between 1 and 6 hours. The process can be carried out in one or multiple batch reactors, possibly fed- batch operation, or in a continuously operating system in one reactor or in a cascade of continuous flow reactors, optionally with multiple feeding points. Though several steps are identified in this document, such as e.g. the absorption step, the reaction step, and the desorption step and indicated as different steps they can be carried out in a single vessel or sometimes steps can be even combined like a reaction and elimination step can be in a reactive separation process in which at least partly they are done simultaneously. The reaction and separation also can involve multiple reaction steps with separation steps in between.

In the large-scale production of chemicals it is preferred to employ a continuous process. The continuous process may be, for example, a single-pass or a recycle process. In a single-pass process, one or more of the reagents pass through the process equipment once, and then the resulting effluent from the reactor is sent for purification or further processing.

The person skilled in the art is capable of selecting the proper reactor and separation unit scheme by determining the overall yield, energy consumption and waste production. Examples:

Materials and Methods:

General: The reactions were carried out in 7 ml_ pressure vessels without stirring. The reactants were charged to the pressure vessels, the vessels were sealed and, for reactions using CO₂, CO₂ was added with a syringe pump. The reaction vessels were placed in an oven and heated to the specified reaction temperature (200 - 280 °C) for the stated reaction time (1 to 6 h). At the end of the reactions, the vessels were cooled to 50 °C and carefully depressurized. The end-cap was opened and a sample of the reaction mixture was solved in H₂O for analysis by Gas Chromatography - Flame Ionization Detector (GC- FID). The results are reported as GC peak area-%. Identity of GC peaks was determined by GC-MS (CI) Gas Chromatography -Mass Spectrometry (Chemical Ionization).

Example 1 Reaction of propanolamine in the presence of CQ2

The reaction of this Example 1 , reacting 2 equivalents of propanolamine (PA) in the presence of CO2, can be represented by below reaction formula:

CMPA UAPPA

L-propanolamine was reacted with CO₂ (molar ratio 1 :1 ) for 1 h at 200 °C, and for 2 h at 250 °C.

The reactions were incomplete at these reaction times/temperatures as starting material was still present. Propanolamine reacts with CO₂ to form the six- membered cyclic carbamate CMPA, which is the main product at 200 °C. CMPA reacts with additional propanolamine to form UAPPA, which is the main product at 250 °C. The results are presented in below Table 1 wherein the amounts for the starting material (PA propanolamine), the intermediate (CMPA) and the product (UAPPA) correspond with GC area%. Table 1 : Reaction of propanolamine with CO₂

It can be concluded that with the right conditions it is possible to react two equivalents of propanolamine in the presence of CO2 to provide a (cyclic urea of) aminopropylpropanolamine

Example 2 Reaction of propanolamine with diethylenetriamine in the presence of CQ2

The reaction of this Example 2, reacting propanolamine (PA) with diethylentriamine (DETA) in the presence of CO2, can be represented by below reaction formula:

OH + DETA For the reaction of DETA with propanolamine 0.52g DETA, 0.37g PA and 0.44g CO2 were charged to the reaction vessels (molar ratio 1 :1 :2). The reaction was carried out for 2 h at 250 °C.

For the reaction of UDETA with propanolamine 1 .3 g UDETA, 0.75 g PA and 0.44 g CO2 were charged to the reaction vessels (molar ratio 1 :1 :1 ) and the reactions were run for 2 h at 280 °C.

The results are presented in below Table 2 wherein the amounts for the starting material (PA, CMPA, and (U)DETA), and the product (DU-(AP-DETA)) correspond with GC area%.

Table 2: Reaction of DETA/UDETA with PA.

It can be concluded that it is possible to react propanolamine with diethylenetriamine in the presence of CO2 to provide a (cyclic diurea of) aminopropylldiethylenetriamine

Example 3 Reaction of propanolamine with ethylenediamine The reaction of this Example 3, reacting propanolamine (PA) with ethylenediamine (EDA) in the presence of CO2, can be represented by below reaction formula:

For the first reaction PA was reacted with an excess EDA and CO2 as CO source. 0.6 g EDA, 0.75 g PA and 0.44 g CO2 were charged to the reaction vessels (molar ratio 1/1/1 ) and the reaction was carried out 280 °C for 4h.

The final reaction mixture was treated to obtain the product amine in a purified quality and unconverted raw material was isolated. 0.50 g of desired product (AP-EU and AE-PU) was obtained per 1 g EDA added to the batch.

0.1 g of the isolated unconverted EDA was transferred to a next batch, to which another 0.5 g EDA was added with 0.75 g PA and 0.44 g CO2 (to obtain a molar ratio EDA:PA: CO2 of 1/1/1 ) and again the reaction was carried out 280 °C for 4h.

The final reaction mixture was treated again to obtain the product amine in a purified quality and unconverted raw material was isolated. Now 0.54 g of desired product (AP-EU and AE-PU) was obtained per 1 g total amount of EDA added. This Example shows the reaction between propanolamine and EDA in the presence of CO2 as a carbon oxide delivering agent to give (two ureas of) aminopropylethyleneamine (aminopropylethyleneurea and aminoethylpropyleneurea). The Example also shows the benefit of recycling materials in the process. Example 4 Reaction of propanolamine with piperazine in the presence of

C02

The reactions of Examples 4A and 4B, reacting propanolamine (PA) with piperazine (PIP) in the presence of CO2, can be represented by below reaction formula:

APP DAPP

For reaction 4A; 0.43 g PIP, 0.375 g PA, and 0.44 g CO₂ (molar ratio PIP/PA/CO2 1/1/2) were charged to a pressure vessel and reacted for 4 h at 220 °C.

For reaction 4B; 0.86 g PIP, 0.75 g PA, 0.22 g CO₂ and 0.18 g H₂O (molar ratio PIP/PA/CO2/H2O 1/1/0.5/1 ) were charged to a pressure vessel and reacted for 4 h at 220 °C.

The results are presented in below Table 4. In Table 4 the amounts for the starting material (PA, CMPA, PIP), and the products (APP, DAPP) correspond with GC area%.

Table 4: Reaction of PIP with PA and CO₂.

Examples 4A and 4B demonstrate that a reaction can also be performed between propanolamine and piperazine. Comparison of the examples also demonstrates that addition of H₂O to the reaction mixture allows a significant reduction in CO₂ amounts and still results in slightly higher yields of the products APP and DAPP.

Example 5: Reaction of piperazine with isopropanolamine in the presence of C02

The reaction of Example 5, reacting isopropanolamine (PA) with piperazine (PIP) in the presence of CO2, can be represented by below reaction formula:

0.43 g piperazine (PIP) was reacted with 0.38 g isopropanolamine (/PA) and 0.44 g CO₂ (molar ratio 1 :1 :2) for 4 h at 220 °C. First, a 5-membered cyclic carbamate of /PA is formed (C/^'MPA) as intermediate from /^'PA and CO2 and this reacts further with piperazine to yield aminoisopropylpiperazine (A/^'PP) as main product along with some aminoisopropylpiperaine carbamate (A/^'PP carbamate). The cyclic urea of aminoisopropylisopropanolamine (UA/^'P/^'PA) is formed in a side reaction from reaction of CM/PA with /^'PA.

Example 6 The reaction of diethylenetriamine urea (UDETA) with isopropanolamine (iPA) in the presence of CQ2

The reaction of Example 6, reacting diethylenetriamine urea (UDETA) with isopropanolamine (iPA) in the presence of CO2 can be represented by below reaction formula

/PA UDETA DU (A/PDETA)

1 .30 g diethylenetriamine urea (UDETA) was reacted with 0.75 g /^'PA and 0.44 g CO2 (molar ratio 1 :1 :1 ) for 4 h at 280 °C to yield the cyclic diurea of aminoisopropyldiethylenetriannine (DU (A/PDETA)) along with the side product UA/P/PA.

Example 7 The reaction of ethylenediamine (EDA) with ethyleneurea (EU) and isopropanolamine

The reaction of Example 7, reacting, ethylenediamine (EDA) with ethyleneurea (EU) and isopropanolamine can be represented by below reaction formula. o O

OH

HN NH Η-,Ν HN O

Η,Ν'

EDA EU /PA EDA CM/PA

AE-/PU A/P-EU

0.45 g ethylenediamine (EDA) and 1 .51 g ethyleneurea (EU) were reacted with 0.75 g /PA (molar ratio 0.75:1 .75:1 ) for 4 h at 280 °C. In this reaction EU functioned as sole CO source. Only little C/^'MPA and some UA/P/PA were formed, while the main products were aminoethyl isopropyleneurea (AE-iPU) and aminoisopropyl ethyleneurea (AiP-EU), whose peaks were not separated by GC and are reported as sum.

The results of Examples 5 to 7 are presented in Table 5 Table 5 Reactions of iPA

The Examples 5 to 7 demonstrate that isopropanolamine forms a cyclic 5- membered carbamate with CO2 and that this cyclic carbamate reacts with amines to elongate these with a branched isopropylamine unit. The reactions were found to occur on the methyl-substituted carbon of the cyclic urea.

The presence of a methyl substituent in the starting material, intermediates and products give rise to a chiral center. Because a racemic mixture of D- and L-2- propanolamine was used as starting material also racemic mixtures of the products were formed. These were sometimes separated during GC analysis, however, enantiomers were not individually assigned and therefore during quantification the peaks of enantiomers were summed up. Example 8 - Reaction of octylamine with propanolamine or isopropanolamine

The reactions of Example 8A and 8B reacting octylamine with propanolamine or isopropanolamine in the presence of CO₂ can be represented by the below reaction formula:

Octyl-UPA

cty - ₂ /PA Octyl-U/PA 0.64 g octylamine was reacted with either 0.38 g propanolamine (8A) or 0.38 g isopropanolamine (8B) and 0.44 g CO₂ (molar ratio 1 :1 :2) for 4 h at 280 °C to yield octyl-proplyeneurea (octyl-UPA) and octyl-isopropyleneurea (octyl-U/PA), respectively, as main products. The results are presented in below Table 6

Table 6 Reactions of octylamine

Examples 8A and 8B demonstrate that the chain elongation of amines with a propanolamine or isopropanolamine units in the presence of carbon dioxide also works for fatty amines. This means that an aminopropyl unit can be added to fatty amines using the process of the invention.

Claims

1 . Process to prepare propylene amines of the formula NH₂-(A-NH-)_PR, wherein R is a hydrogen atom or an alkyl group, p is at least 1 when R is an alkyl group, and at least 2 when R is a hydrogen atom, or derivatives or precursors thereof wherein one or more units -NH-A-NH- may be present as a cyclic urea unit

or a cyclic unit

r between two units -NH-A-NH- a carbonyl bond is present, each unit -A- can be independently an alkylene unit and at least one unit - A- is a -C3H_6- unit, wherein each -C3H6- unit can be linear or branched, by reacting (i) at least one of a hydroxy-functional compound chosen from the alkanolamine-functional compounds, and dihydroxyalkylene compounds, with (ii) an amine-functional compound, in the presence of (iii) a carbon oxide delivering agent, wherein at least one of the alkanolamine-functional compound, the amine-functional compound and/or the carbon oxide delivering agent contains at least one alkylene unit (A) that is a propylene unit.

Process of claim 1 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 0.6 to 1 .

Process of claim 2 wherein the molar ratio of carbon oxide delivering agent to amine functional compound is between 0.7:1 and 20:1 .

4. Process of claim 1 , wherein the molar ratio of hydroxy-functional compound to amine-functional compound is at least 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 0.05:1 .

5. Process of claim 4 wherein the molar ratio of hydroxy-functional compound to amine-functional compound is between 0.8 and 5:1 and the molar ratio of carbon oxide delivering agent to amine functional compound is between 0.2:1 and 20:1 .

6. Process of claim 4 or 5.wherein the molar ratio of hydroxy-functional compound to amine-functional compound is between 1 :1 and 2:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is between 0.7:1 and 3:1

7. Process of claim 1 , wherein the molar ratio of hydroxy-functional compound to amine-functional compound is between 0.05:1 and 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is higher than the molar ratio of hydroxy-functional compound to amine- functional compound.

8. Process of claim 7 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 10% higher than the molar ratio of hydroxy-functional compound to amine-functional compound.

9. Process of any one of the preceding claims wherein the alkanolamine- functional compound and the carbon oxide delivering agent are at least partly added as one compound by using a carbamate adduct.

10. Process of any one of the preceding claims wherein the amine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using an urea adduct.

1 1 . Process of any one of the preceding claims wherein the amine functional compound is a primary amine or a cyclic secondary amine compound.

12. Process of any one of the preceding claims wherein the amine-functional compound is of the formula R-NH₂ and R is an alkyl group containing 6 to 22 carbon atoms

13. Process of any one of the preceding claims wherein next a step is performed to convert the obtained cyclic alkylene urea into its corresponding propylene amine.

14. Process of any one of the preceding claims wherein the alkanolamine- functional compound is of the formula OH-(A-NH-)_qH wherein q is at least 1 and the amine-functional compound is of the formula NH₂-(A-NH-)_rH wherein r is at least 1 , wherein the sum of q+r is at least 2 and wherein optionally one or more q or r units may be present as a cyclic alkylene urea,

— N N- cyclic alkylene carbamate or cyclic unit

15. Process of claim 14 wherein the hydroxy-functional compound, the amine- functional compound do not contain cyclic units and react in the presence of water, with a molar ratio of water : carbon oxide delivering agent of from 0.01 :1 to 2:1 .

16. Process of claim 15 wherein the molar ratio of water : carbon oxide delivering agent is between 0.05:1 and 1 :1 .

17. Process to prepare propyleneamines of any one of preceding claims wherein if the amine-functional compound is a compound containing a

terminal cyclic unit , i.e. a compound containing the above cyclic unit wherein at least one nitrogen is bound to a hydrogen atom, the process of the present invention is preferably performed in a liquid that contains water.

18. Process of claim 17 wherein the liquid comprises at least 75 wt-% of water on total liquid weight.

19. Process of claims 17 or 18 wherein the molar ratio of water to the amine- functional compound is greater than 0.2:1 , preferably greater than 0.5:1 and most preferably greater than 1 :1 .

20. Process according to any one of the preceding claims wherein water is added or removed during the process intermittently, semi-continuously or continuously.

21 . Process of any one of preceding claims wherein in a preceding step a carbon oxide delivering agent is manufactured that is a cyclic urea adduct of an alkyleneamine or the alkanolamine that comprises at least one -NH-A- NH- moiety and at least two alkylene moieties, wherein at least one of the units A and alkylene units is a propylene unit, wherein the alkyleneamine or alkanolamine compound is reacted with CO2 in the presence of an auxiliary compound selected from ethylenediamine (EDA), propylenediamine (PDA), monoethanolamine (MEA), monopropanolamine (MPA) and mixtures thereof, the molar ratio of auxiliary compound to amine-functional compound being at least 0.02:1 .

22. Process of any one of preceding claims wherein in a preceding step a carbon oxide delivering agent is manufactured that is a cyclic urea adduct of an alkyleneamine compound, the alkyleneamine compound having a linear -NH-A-NH- group to be used as the carbon oxide delivering agent, comprising the steps of

in an absorption step contacting a liquid medium comprising an alkyleneamine compound having a linear -NH-A-NH- group with a CO2- containing gas stream at a pressure of 1 -20 bar, resulting in the formation of a liquid medium into which CO2 has been absorbed,

bringing the liquid medium to cyclic urea formation conditions, and in an urea formation step forming cyclic urea adduct of the alkyleneamine compound, urea formation conditions including a temperature of at least 120°C, wherein the total pressure at the end of the urea formation step is at most 20 bar, wherein the temperature in the absorption step is lower than the temperature in the urea formation step.

23. Process of any one of preceding claims wherein a mixture of straight-chain higher propyleneamines and non-straight-chain higher propyleneamines selected from branched higher propyleneamines and cyclic higher propyleneamines, or the urea derivatives thereof is manufactured, comprising the step of reacting amine-functional compound with alkanolamine-functional compound in the presence of a carbon oxide delivering agent, wherein

- amine-functional compound comprising a combination of straight-chain amine-functional compound and non-straight-chain amine-functional compound is reacted with straight-chain alkanolamine-functional compound, or

- straight-chain amine-functional compound is reacted with alkanolamine- functional compound comprising a combination of straight-chain alkanolamine-functional compound and non-straight-chain alkanolamine- functional compound, or

- amine-functional compound comprising a combination of straight-chain amine-functional compound and non-straight-chain amine-functional compound is reacted with alkanolamine-functional compound comprising a combination of straight-chain alkanolamine-functional compound and non-straight-chain alkanolamine-functional compound.

24. Process of any one of the preceding claims where in the process is performed as an integrated process comprising the steps of

- in a reaction step reacting a hydroxy-functional compound selected from the group of alkanolamines, dihydroxyethane and dihydroxypropane with an amine-functional compound, wherein at least part of the total of hydroxy-functional compounds and amine-functional compounds is provided in the form of a CO2 adduct, to form CO2 adduct of a product propyleneamine compound,

- in an elimination step converting CO2 adduct of polypropylene amine compound to the corresponding product propylene amine compound, wherein a fraction comprising a recycle compound comprising a -NH-A- NH- moiety or a -NH-A-OH moiety, or HO-A-OH, or CO2 adducts thereof, is provided from the end of the reaction step or the elimination step to the adduction step or to the reaction step,

the recycle compound having per molecule on average fewer of the total of -NH-A-NH- moieties and -NH-A-OH moieties than the product propyleneamine compound.